超临界CO2快速膨胀法制备SiO2/聚氨酯超疏水涂层

用超临界CO₂快速膨胀法制备了SiO₂/聚氨酯超疏水涂层。首先用十三氟辛基三乙氧基硅烷（F-硅烷）和γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷（KH-570）改性纳米二氧化硅,制备出含双键的纳米二氧化硅粒子,将其分散在超临界CO₂中,再利用超临界CO₂快速膨胀法将其喷射到双键封端的且已添加了引发剂的聚氨酯涂层表面,通过加热,使纳米二氧化硅粒子接枝在聚氨酯涂层表面,形成稳固粗糙结构,获得了超疏水性质。研究了喷嘴温度、反应釜温度和压力、偶联剂配比、表面粗糙度对涂层疏水性的影响。结果表明：涂层的静态水接触角可达到169.1°±0.6°;在喷嘴和釜内温度都为90℃,釜内压力为16 MPa,F-硅烷和KH-570配比为1∶1,表面粗糙度为7.3 μm时,所制得涂层具有较好的超疏水性,且具有优良的耐刮伤性。该法高效环保,涂层性能优良,适于大面积制备。     

改性纳米SiO2/聚氨酯-含氟丙烯酸酯无皂乳液合成及其胶膜性能表征

引言水性聚氨酯相对溶剂型聚氨酯具有不燃、气味小、不污染环境等优点[1-2],从而广泛用于涂料[3]、胶黏剂[4]、油墨[5]等领域。目前,常用于软包装领域的薄膜主要是表面能很低的非极性膜,而水性聚氨酯胶黏剂具有较高的表面自由能,对非极性膜的润湿性差,因此需要降低水性聚氨酯的表面张力,达到润湿非极性膜的目的。     

核壳型纳米SiO2/含氟聚丙烯酸酯复合乳液的合成与表征

采用原位乳液聚合法,在可聚合阴离子乳化剂/非离子乳化剂复配体系下,以γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH-570)改性的纳米SiO2、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸(AA)等为核相组成,以MMA、BA及甲基丙烯酸十二氟庚酯(DFMA)为壳相单体,合成纳米SiO2/含氟聚丙烯酸酯复合乳液.考察了纳...     

纳米二氧化硅复合涂料的制备及其性能

通过表面改性技术制备了疏水性的纳米二氧化硅粒子,粒径约50 nm.在机械搅拌和超声场共同作用下,将纳米二氧化硅均匀分散到聚氨酯清漆中,制得纳米二氧化硅复合涂料,考察了纳米二氧化硅复合量对复合涂料性能的影响.直接腐蚀实验、阳极极化和交流阻抗测试结果表明,加入偶联剂改性的纳米二氧化硅后,复合聚氨酯清漆在氯化钠溶液中的抗腐蚀能力明显提高,浸泡腐蚀失重量减小约20％～70％,阳极腐蚀电流降低1个数量级以上,低频区涂层阻抗值增大2个数量级以上.油漆剪切强度和剥离强度实验显示,纳米复合漆膜的附着力增加.     

Effect of acrylic acid and hydroxyethyl methacrylate modified nano-SiO2 particles on poly(methyl methacrylate-hydroxyethyl methacrylate) soap-free emulsion polymerization

Nano-SiO₂ powder was modified with acrylic acid (AA) and hydroxyethyl methacrylate (HEMA), respectively. The kinetics of the soap-free emulsion polymerization of methyl methacrylate (MMA) and HEMA in the presence of unmodified or modified nano-SiO₂ particles was investigated. The structure of the nano-SiO₂ particles and the Poly(MMA-HEMA) composite emulsion was characterized by Fourier transform infrared spectroscope (FT-IR). The particle size and size distribution of the emulsion, the morphology of emulsion particle, the surface tension, and ionic conductivity of these systems before and after polymerization were determined. The IR spectra showed that the organic modifiers were incorporated onto the surface of the nano-particles. In addition, the solid content and monomer conversion of the Poly(MMA-HEMA) composite emulsion with modified nano-SiO₂ are higher than that with original inorganic particles. The particle size became smaller and the particle distribution narrowed after applying the modified nano-SiO₂ particles. The SEM observation demonstrated that the shapes of these emulsion particles were uniform sphere. The surface tension and ionic conductivity increased significantly after polymerization.     

Preparation and study of stable fluorine-free superhydrophobicity of cotton fibers

This paper proposes a method of directly modifying the surface of cotton fiber to achieve super-hydrophobic properties. The process was directly utilized the long-chain alkyl siloxane and the nano-SiO₂ modified cotton cloth, which was simple to operate, low in cost and environmentally friendly. This study discussed the influence of solvent ratio, reactant content and ammonia content on hydrophobicity. The solvent ratio had the greatest influence, and the maximum water contact angle (CA) changes were70° ± 1°. The maximum water CA of the superhydrophobic cotton fabric prepared after process selection was 162 ± 1.5°; it had good acid, alkali and salt resistance. After 24 h in a solution with a pH of 1–14, CA remained almost unchanged; After 144 h in a 3.5% salt solution, CA stabilized above 132°; it had self-cleaning properties; it had good selective adsorption performance, which can quickly separate oil and water; it had good mechanical stability. After 300 times abrasion of sandpaper, which still shows hydrophobic properties.     

高性能水性UV固化聚氨酯的合成与性能研究

用环氧丙烯酸酯(EA)、羟基硅油合成了环氧/有机硅改性水性光固化聚氨酯乳液(WPU);研究了EA、羟基硅油、亲水扩链剂二羟甲基丁酸(DMBA)的用量,中和度和硅烷偶联剂的添加量对乳液和涂膜性能的影响。用红外光谱和接触角测量仪对树脂进行表征。结果表明:通过EA、羟基硅油改性的水性光固化聚氨酯涂膜的硬度高、附着力强、耐水性较好,克服了未改性水性光固化聚氨酯的缺点。当EA用量为4%、羟基硅油为2%、DMBA为8%、中和度为80%、硅烷偶联剂的添加量为1%时,水性光固化聚氨酯乳液的综合性能较好,树脂接触角大大提高。     

高疏水性硅橡胶防污闪涂料的制备及其性能研究

以端羟基聚二甲基硅氧烷、不同粒径的改性二氧化硅粒子、硅烷偶联剂及助剂为原料,采用有机-无机杂化纳米技术,制得具有高疏水性能的室温硫化(RTV)硅橡胶防污闪涂料。采用扫描电镜表征了涂层的表面形貌,用静态接触角测试仪测定了二氧化硅用量对涂层的憎水性及憎水迁移性变化。结果表明,固定纳米级二氧化硅的用量,当微米级二氧化硅用量为10份时,涂层表面形成一定的微米二级粗糙结构,涂层表面接触角为131.50,具有较高的疏水性能;同时,涂层也具有优良的憎水迁移性。此时,硅橡胶的拉伸强度为2.08 MPa,伸长率581%,撕裂强度5.65 kN/m,体积电阻率1.38×1015Ω·m,污秽湿工频闪络电压3 kV,阻燃性FV-0级。     

硅烷偶联剂表面改性二氧化钛粒子超疏水性能研究

针对无机二氧化钛（TiO2）粒子在有机体系中的分散性问题,采用硅烷偶联剂KH-570对无机填料钛白粉（二氧化钛,TiO2）的表面进行有机化改性;并通过红外光谱（FT-IR）、接触角测试、沉降实验、扫描电子显微镜（SEM）等手段表征表面改性TiO2粒子的结构,测试其超疏水性能,分析超疏水表面形成的机理。结果表明,经KH-570表面改性的TiO2粒子的疏水性和分散性得到明显改善,当KH-570质量分数达到15%时,表面改性的TiO2涂层与水的静态接触角达152.5˚,表现出良好的超疏水性能。     

Application of EIS and salt spray tests for investigation of the anticorrosion properties of polyurethane-based nanocomposites containing Cr2O3 nanoparticles modified with 3-amino propyl trimethoxy silane

The Cr₂O₃ nanoparticles were modified with 3-amino propyl trimethoxy silane in order to obtain proper dispersion and increment compatibility with the polyurethane coating matrix. The nanocomposites prepared were applied on the St-37 steel substrates. The existence of 3-amino propyl trimethoxy silane on the surface of the nanoparticles was investigated by Fourier transform infrared (FTIR) spectroscopy and thermal gravimetric analysis (TGA). Dispersion of the surface modified particles in the polyurethane coating matrix was studied by a field emission-scanning electron microscope (FE-SEM). The electrochemical impedance spectroscopy (EIS) and salt spray tests were employed in order to evaluate the corrosion resistance of the polyurethane coatings. Polarization test was done in order to investigate the corrosion inhibition properties of the Cr₂O₃ nanoparticle on the steel surface in 3.5 wt.% NaCl solution. The adhesion strengths of the coatings were evaluated by pull-off adhesion tester before and after 120 days immersion in 3.5 wt.% NaCl solution. FT-IR and TGA analyses revealed that surface modification of the nanoparticles with 0.43 silane/5 g pigment resulted in the greatest amount of silane grafting on the surface of particles. Results obtained from FE-SEM analysis showed that the surface modified nanoparticles dispersed in the coating matrix properly. Results obtained from EIS and salt spray analyses revealed that the surface modified particles enhanced the corrosion protection performance of the polyurethane coating considerably. The improvement was more pronounced for the coating reinforced with 0.43 g silane/5 g pigment. Moreover, the adhesion loss decreased in the presence of surface modified nanoparticles with 0.43 silane/5 g pigment.     

原位聚合法制备纳米TiO2/有机硅改性丙烯酸酯复合乳液

用硅烷偶联剂对纳米二氧化钛(TiO2)粒子表面进行预处理，使其表面由亲水性变为疏水性，并在其表面接枝上可反应的有机官能团。通过改性纳米TiO2表面上的原位聚合反应，制备了纳米TiO2／硅丙复合乳液。透射电子显微镜观察结果显示，乳液中存在两种结构的乳胶粒子：一种是以聚丙烯酸酯为核、有机硅聚合物为壳的核壳结构硅丙乳胶粒子；另一种是以纳米TiO2为核、有机聚合物为壳的纳米TiO2／聚合物复合结构乳胶粒子。乳胶粒子的结构形态可由乳化剂的用量控制。该复合乳液具有较好的杀菌效果，在较短时间内对细菌的杀灭率可达90％以上。     

Robust super-hydrophobic ceramic coating on alumina with water and dirt repelling properties

Artificial super-hydrophobic surfaces are required for various applications. The super-hydrophobic surfaces are usually made by applying a low surface-energy organic coating on a highly textured substrate. A major problem with the as-created surfaces is their poor durability. This problem is even severer for the surfaces created by applying the organic coating on inorganic substrates. The present study reports for the first time the all-inorganic super-hydrophobic surface created by modifying the inorganic substrates with polymer-derived inorganic coating. A polydimethylsiloxane (PDMS) film was applied to an alumina substrate having flower-like hierarchal micro-nano surface texture, and then subjected to pyrolysis at 400°C in a nonoxidizing atmosphere. As a result, a Si_xC_yO_z ceramic coating with low-surface energy methyl groups was formed on the alumina substrate. The as-modified alumina exhibited super-hydrophobicity with a water contact angle of 170° and a sliding angle of 5°. The super-hydrophobicity was well retained after abrasion with sandpaper and exposure to boiling water and acidic solution. The super-hydrophobic alumina demonstrated desired water repelling and self-cleaning function. The method explored in this study could also be used for super-hydrophobic surface modification of other inorganic materials such as glass and metals.     

Pickering emulsion polymerization: Preparation of polystyrene/nano-SiO2 composite microspheres with core-shell structure

Polystyrene/nano-SiO₂ composite microspheres (PS/nano-SiO₂) with core-shell structure were successfully synthesized in a Pickering emulsion route using nano-SiO₂ particles as stabilizers, which were organically modified by methacryloxypropyltrimethoxysilane (MPTMS) which containing a reactive CC bond. The products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), fourier transformation infrared spectrum (FTIR), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). In addition, bare PS spheres could also be obtained by changing synthetic conditions. It was found that the morphology of the resulting products depends on particle concentration, particle wettability and pH value of particle dispersion. A possible mechanism for the formation of the composites with different morphologies is proposed.     

PUFA织物整理剂的制备及性能表征

通过溶液聚合相转化法制得一种新型聚氨酯改性氟代聚丙烯酸酯乳液(PUFA)。通过红外光谱、热失重分析、透射电镜及扫描电镜对乳液粒子的形态、胶膜的热稳定性及纤维上的膜形貌进行了观察,并对其易去污的应用性能进行了分析。研究结果表明,聚氨酯链段的引入使乳液具有良好的热稳定性,聚合物能在纤维表面形成一层光滑且有优异疏水性的膜,接触角可达123°,能使整理后棉织物的疏水性达到87分,疏油等级6级,易去污可达到5级。     

Hydrophobic composite coatings with photocatalytic self-cleaning properties by micro/nanoparticles mixed with fluorocarbon resin

A newly developed hydrophobic composite coating was fabricated by incorporating modified TiO₂ nanoparticles and hydrophobic material polytetrafluoroethylene (PTFE) micropowders dispersed in fluorocarbon resin. Moreover, the surface characteristics and self-cleaning properties of the newly developed composite material were examined. The material was found to exhibit sufficient hydrophobicity with a water contact angle of 133°. The surface free energy of the composite coating was 4.11 mJ/m². Scanning electron microscopy results revealed a micro/nanocomposite structure composed of PTFE micropowders and TiO₂ nanoparticles, which was verified by X-ray photoelectron spectroscopy results. Through ultraviolet irradiation the modified TiO₂-PTFE/FEVE composite coating successfully removed oleic acid absorbed on its surface. These results showed that the functional composite coating had a sufficiently hydrophobic surface with an efficient self-cleaning effect.     

高含量有机硅改性水性聚氨酯乳液的制备及性能研究

合成了高有机硅含量的水性聚氨酯稳定乳液。测量了有机硅含量对水接触角的影响,并对乳液的稳定性、黏度及涂膜的FT-IR、DSC、机械性能等进行了表征。     

氨基硅油微乳液改性水性聚氨酯的合成和性能

合成了水性聚氨酯乳液和氨基硅油(AEAPS)微乳液改性水性聚氨酯乳液,研究了两种水性聚氨酯的性能及在织物上的涂层效果。结果表明,当氨基硅油相对于聚丙二醇的质量百分比为8.18%时,有机硅改性水性聚氨酯乳液的离心稳定性好,乳液胶膜表面硅原子的质量分数为0.92%;该有机硅改性水性聚氨酯软段相与硬段相的微观相分离增大,乳液胶膜的耐水性能和热稳定性提高;该有机硅改性水性聚氨酯乳液作为织物涂层剂时,可以赋予织物柔软、滑爽的风格。     

Effect of surface microstructure on the hydrophobicity of coatings

In this paper, coatings adopted SiO₂ nanoparticles ranging from 1 wt% to 7 wt% were in situ polymerized with low surface energy polymer, and different surface microstructures were built automatically during painting film. Copper microstructure surface was also achieved by chemical etching method and then was modified by low surface energy resin as contrast. The contact angle and the peel strength between the coating and bio-gooey simulacrum were studied. The results showed that the hydrophobicity of the coating was remarkably affected by the surface microstructure. The coating containing 5 wt% SiO₂ nanoparticles was covered with micro- and nano-scale salience and holes, and had the maximum contact angle and the minimum peel strength. Copper slices presented uniform micron and sub-micron structure surface when etching for 15 min and the contact angle reached a maximum of 125° after being modified.     

Preparation of HMDS-modified silica/polyacrylate hydrophobic hard coatings on PMMA substrates

Colloidal silica nanoparticles synthesized from tetraethoxysiliane via a sol–gel process were surface modified by 3-(trimethoxysilyl)propyl methacrylate (MSMA) and 1,1,1,3,3,3-hexamethyldisilazane (HMDS). MSMA acted both as a C=C provider and a coupling agent, whereas HMDS was used to prevent particle aggregation and engender hydrophobicity. The modified silica particles (HMSiO₂) were UV-cured together with the crosslinking agent, dipentaerythritol hexa-acrylate (DPHA) to form coatings on poly(methyl methacrylate) (PMMA) substrates. Dynamic light scattering of the synthesized sols indicated that the average size of HMSiO₂ was ca. 10 nm, consistent with that obtained from TEM imaging. FTIR spectroscopic analyses demonstrated chemical attachment of HMDS to the silica particles. The cured coatings were characterized in terms of water contact angle, light transmittance, hardness, abrasion resistance, and surface morphology. It was found that hydrophobicity of the coatings increased while light transmittance and hardness decreased with increasing HMDS content. DPHA played the role of providing mechanical strength and adherence; however, the coatings became lightly hazy when the weight ratio of DPHA/silica fell in the range 0.3–0.7. In the optimal case, a hard coating (4H) with water contact angle of 108° and transmittance of ~100% (vs PMMA) had been obtained at the DPHA content of 10 wt%.     

氟硅改性无溶剂环氧涂料的制备与性能

采用甲基丙烯酸十三氟辛酯（TFM）改性氨基硅油（AS）制备氟化氨基硅油（FAS）,并用其改性环氧树脂（EP）探究氨基硅油及氟化氨基硅油添加量对环氧涂层性能的影响。本文通过红外光谱对改性结果进行表征,通过柔韧性测试、画圈附着力测试、铅笔硬度测试、耐冲击测试、热失重测试、接触角测试、紫外加速老化实验和Tafel极化曲线测试,分别评价涂层的柔韧性、附着力、硬度、耐冲击性、耐热性、疏水性、耐候性和防腐性能,通过扫描电镜对涂层断面进行分析,并通过EDS对涂层进行表面元素分析。结果表明,氟添加量为15%制备氟化氨基硅油改性环氧树脂时,氟硅改性EP涂层相对于未改性EP涂层,硬度由2H提升至3H,附着力由2级提升至1级,柔韧性由1mm提升至0.5mm,耐冲击由45cm提升至50cm,热稳定性增强,接触角由70.5°提升至123°,耐紫外老化（432h）由3级提升至1级,E_corr由-0.6187V正移至-0.1720V,I_corr由1.9858×10^-8A/cm²减小至3.7125×10^-10A/cm²。适量氟化氨基硅油的引入,显著提升了环氧涂层的机械性能、耐候性能和防腐性能。